Combined Experimental and Molecular Simulation Investigation of the Individual Effects of Corexit Surfactants on the Aerosolization of Oil Spill Matter.

We report laboratory aerosolization experiments and classical molecular dynamics (MD) simulations, with the objective of investigating the individual effects of the two Corexit surfactants Span 80 (nonionic) and dioctyl sodium sulfosuccinate (DOSS, ionic), on the aerosolization of oil spill matter to the atmosphere. Our simulation results show that Span 80, DOSS, and the oil alkanes n-pentadecane (C15) and n-triacontane (C30) exhibit deep free energy minima at the air/seawater interface. C15 and C30 exhibit deeper free energy minima at the interface when Span 80 is present, as compared to the situation when DOSS or no surfactants are at the interface. These results suggest that Span 80 makes these oil hydrocarbons more likely to be adsorbed at the surface of seawater droplets and carried out to the atmosphere, relative to DOSS or to the situation where no surfactants are present. These simulation trends are in qualitative agreement with our experimental observations in a bubble-column setup, where larger amounts of oil hydrocarbons are ejected when Span 80 is mixed with oil and injected into the column, as compared to when DOSS is used. Our simulations also indicate that Span 80 has a larger thermodynamic incentive than DOSS to move from the seawater phase and into the air/seawater interface. This observation is also in qualitative agreement with our experimental measurements, which indicate that Span 80 is ejected in larger quantities than DOSS. Our simulations also suggest that DOSS predominantly adopts a perpendicular orientation with respect to the air/seawater interface at a dispersant to oil ratio (DOR) of 1:20, but has a slight preference to lie parallel to the interfaces at a DOR = 1:5; in both cases, DOSS molecules have their tails wide open and stretched. In contrast, Span 80 has a slight preference to align parallel to the interfaces with a coiled conformation at both DOR values.

Bubble bursting as an aerosol generation mechanism during an oil spill in the deep-sea environment: laboratory experimental demonstration of the transport pathway.

Oil spills in the deep-sea environment such as the 2010 Deep Water Horizon oil spill in the Gulf of Mexico release vast quantities of crude oil into the sea-surface environment. Various investigators have discussed the marine transport and fate of the oil into different environmental compartments (air, water, sediment, and biota). The transport of the oil into the atmosphere in these previous investigations has been limited to only evaporation, a volatility dependent pathway. In this work, we studied the aerosolization of oil spill matter via bursting bubbles as they occur during whitecaps in a laboratory aerosolization reactor. By evaluating the alkane content in oil mousse, crude oil, the gas phase, and particulate matter we clearly demonstrate that aerosolization via bursting bubbles is a solubility and volatility independent transport pathway for alkanes. The signature of alkane fractions in the native oil and aerosolized matter matched well especially for the less volatile alkanes (C20-C29). Scanning electron microscope interfaced with energy dispersive X-ray images identified the carbon fractions associated with salt particles of aerosols. Theoretical molecular dynamics simulations in the accompanying paper lend support to the observed propensity for alkanes at air-salt water interfaces of breaking bubbles and the produced droplets. The presence of a dispersant in the aqueous phase increased the oil ejection rate at the surface especially for the C20-C29 alkanes. The information presented here emphasizes the need to further study sea-spray aerosols as a possible transport vector for spilled oil in the sea surface environment.

Bubble bursting as an aerosol generation mechanism during an oil spill in the deep-sea environment: molecular dynamics simulations of oil alkanes and dispersants in atmospheric air/salt water interfaces.

Potential of mean force (PMF) calculations and molecular dynamics (MD) simulations were performed to investigate the properties of oil n-alkanes [i.e., n-pentadecane (C15), n-icosane (C20) and n-triacontane (C30)], as well as several surfactant species [i.e., the standard anionic surfactant sodium dodecyl sulfate (SDS), and three model dispersants similar to the Tween and Span species present in Corexit 9500A] at air/salt water interfaces. This study was motivated by the 2010 Deepwater Horizon (DWH) oil spill, and our simulation results show that, from the thermodynamic point of view, the n-alkanes and the model dispersants have a strong preference to remain at the air/salt water interface, as indicated by the presence of deep free energy minima at these interfaces. The free energy minimum of these n-alkanes becomes deeper as their chain length increases, and as the concentration of surfactant species at the interface increases. The n-alkanes tend to adopt a flat orientation and form aggregates at the bare air/salt water interface. When this interface is coated with surfactants, the n-alkanes tend to adopt more tilted orientations with respect to the vector normal to the interface. These simulation results are consistent with the experimental findings reported in the accompanying paper [Ehrenhauser et al., Environ. Sci.: Processes Impacts 2013, in press, (DOI: 10.1039/c3em00390f)]. The fact that these long-chain n-alkanes show a strong thermodynamic preference to remain at the air/salt water interfaces, especially if these interfaces are coated with surfactants, makes these species very likely to adsorb at the surface of bubbles or droplets and be ejected to the atmosphere by sea surface processes such as whitecaps (breaking waves) and bubble bursting. Finally, the experimental finding that more oil hydrocarbons are ejected when Corexit 9500A is present in the system is consistent with the deeper free energy minima observed for the n-alkanes at the air/salt water interface at increasing concentrations of surfactant species.